Supersensitization of photographic emulsions using triazines



July 19, 19 0 B CAR'ROLL ETAL 2,945,762

SUPERSENSITIZATION 0F PHOTOGRAPHIC EMULSIONS usmc TRIAZINESI Filed Oct.12, 1955 Fig. I

300 400 500 l 600 700 A= 3,3" DIETHYLOXATHIADICARBOCYANINE IODIDEB=3,3"DIETHYLOXATHIADICARBOCYANINE looms WITH 4,4- B|s [4'6"SULFOANIUNOI6'j5' HYDROXYETHYLAMINO TRIAZIN "Z'YLAMINO] STILBENE2,2"DISULFONIC ACIDIII! IILPI'ITFTMIIH I'I'ITIIN 300 4-00 $00 600 700 C =3,3"D'IETHYLOXATHIADICARBOCYANINE IODIDE WITH 4,4'- BIS(4,6'DIANILINO' S'TRIAZIN'ZYLAMINO) STILBENE" 2,2 DISULFONIC ACID llll IU/IITWWIIIIIUIllkllll 300 400 500 600 700 I D= 3,3" DIETHYLOXATHIADICARBOCYANINEIODIDE WITH 4, 4"

BIS (4' PHENOXY -6- P HYDROXYETHYLAMINO'S' TRIAZIN "2' YLAMINO) STILBENE"2,2" DISULFONIC ACID Fig.3

Bar! 11. Carroll Jean E. Jones John Jjuence INVENTORY ATTO RNEY-Sstilbene compounds.

United States Patent SUPERSENSITIZA'IION 0F PHOTGGRAPHIC EMULSIONS USINGTRIAZKNES Filed on. 12, 1955, Ser. No. 540,052

16 Claims. (11. 96-100) This invention relates to photographic silverhalide emulsions useful in color photography and photographic silverhalide emulsions containing certain dicarbocyanine dyes, and assupersensitizers therefor, bis-tri azinylamino- It is known in the artof making photographic emulsions that certain dyes of the cyanine classalter the sensitivity of photographic emulsions of thegelatino-silverhalide kind, when the dyes are incorporated in theemulsions. It is also known that the sensitization produced by a givendye varies somewhat with the type of emulsion in which the dye isincorporated. Furthermore, the sensitization of a given emulsion by agiven dyemay be altered by varying the conditions in the emulsion. Forexample,

the sensitization may be increased by increasing the silver ionconcentration or decreasing the hydrogen ion concentration (i.e.,increasing the alkalinity) or both. Thus,

sensitization can be increased by bathing plates, coated with aspectrally sensitized emulsion, in Water or in aqueous solutions ofammonia. Such a process'of altering the sensitivity of a sensitizedemulsion by increasing the silver ion concentration and/orby decreasingthe hydrogen ion concentration is commonly called hypersensitization.Hypersensitized emulsions have generally poor keeping qualities.

We have now found another means of altering the sensitivity in emulsionscontaining certain dicarb-ocyanine dyes. Since the conditions in theemulsions, ,i.e., the hydrogen ion and/ or the silver ion concentrationundergo little or no change in our method, We shall designate our methodas a kind of supersensitization.

It is, therefore, an object of our invention to provide photographicemulsions containing'certain dicarbocyanine dyes and, assupersensitizers therefore, bis-triazinylaminoa stilbene compounds.Another object is to provide a means for preparing these supersensitizedemulsions.

Still another object is to provide photographic emulsions containingbis-triazinylaminostilbene compounds which are especially useful incolor photography. Other objects will become apparent from aconsideration of the following description and examples.

The dicar-bocyanine dyes which are useful in practicing our inventioncan advantageously'be represented by the following general formula:

taining from to 6 atoms in the heterocyclic ring, e.g.,

2,945,762 Patented July 19, 1&60

"ice

7 '2 v a heterocyclic nucleus of the benzothiazole series (e.g.,benzothiazole, 4-chlorobenzothiazole, S-chlorobenzothiazole,6-chlorobenzothiazole, 7-chlorobenzothiazole, 4- methylbenzothiazole,S-methylbenzothiazole, 6-Inethylbenzothiazole, S-bromobenzothiazole,6-bromobenzothiazole, 4-phenylbenzothiazole, S-phenylbenzothiazole, 4-methoxybenzothiazole, S-methoxybenzothiazole, 6-methoxybenzothiazole,6-iodohenzothiazole, 5 -iodobenzotl1iazole, 4-ethoxybenz-othiazole,S-ethoxybnzothiazole, 5,6- dimethylbenzothiazole,S-hydroxybenzothiazole, 6-hydroxybenzothiazole, etc.), av heterocyclicnucleus of the naphthothiazole' series (e.g., t-naphthothiazole,fi-naphthothiazole, 7-methoxy-n-naphthothiazole,8-methoxy-anaphthothiazole, 5-methoxy-fl-naphthothiazole,S-ethoxya-naphthothiazole, etc.), a heterocyclic nucleus of thebenzoselenazole series i(e.g .,ibenzoselenazole,S-chlorobenzoselenazole, 6-methoxybenzoselenazole,S-methoxybenzoselenazole, etc.) a heterocyclic nucleus of thenapthoselenazole series (e.*g., a-naphthoselenazole, B-naphthoselenazole, etc.), a heterocyclic nucleus of the benzoxazoleseries (e.g., benzoxazole, 5-hydroxybenzoxazole, 6-hydroxybenzoxazole,'5-chlorobenzoxazole, 5- methoxybenzoxazole, 6-methoxybenzoxazole, 5-phenylbenzoxazole, S-bromobenzoxazole, etc.), and a heterothoxazole,fi-naphthoxazole, etc.), and Z represents the non-metallic atomsnecessary to complete a heterocyclic above),'a heterocycl-ionucleus ofthebenzoselenazole 5-chlorobenzimidazole,

nucleus selectedfrom the group consisting of a heterocyclic nucleus ofthe benzoxazole series (e.g., such as those defined by Z. above), 'aheterocyclic nucleusrof the naphthoxazole series (e.g., such as thosedefined by Z series (eLg., such as thosev defined by Z above),'aheterocyclic nucleus ofthe naphthoselenazoleseries (e.g., such as thosedefined by Z above), a heterocyclic nucleus of the naphthothiazoleseries (e.g., such as those defined by Z above), a heterocyclic nucleusof the Z-quinoline series Z-quinQline, 6-methyl-2-quinoline, 7-methyl-2-quinoline, 8-methyl-2-quinoline, 6-chloro-2-quinoline, 8-chloro-Z-quinoline, 4-chloro-2-quinoline, S-ethoxy-Z-quinoline,'6-ethoXy-2-quinoline, 7,-ethoXy-2-quinoline, 6-hydrOxy-Z-quinoline, 7-hydroxy-2-quinoline, 6-methoxy-2- quinoline, etc.), a heterocyclicnucleus of the 4,-quinoline series (e.g., 4-q-uinoline,6-methoxy-4-quinoline, 7-methyl- 4-quinoline, 8-methyl-4-quinoline,etc.), a heterocyclic nucleus of the benzimidazole series (e.g.,benzimidazole,

5,6-dichlorobenzimidazole, 1,7- trimethylenebenzimidazole, etc.), and aheterocyclic nucleus of the 5,6-benzoquinoline series (e.g.,5,6-benz'o-2- quinoline, etc.).

The bis-triazinylam-inostilbene compounds useful in practicing ourinvention have been previously employed in the 'art as fluorescentagents and as bleaching (optical) agents, and hence are widely knownsubstances. Especially useful compounds of this class comprise thosecompounds represented by the following general formula:

N N t r r thio, ethylthio,'etc.), an arylthio group (e.g., 'pl1enylthio,

tolylthio, etc.), a heterocyclylthio group (e.g.,;-benzothiazylthio,etc.), an amino group, an 'alky-lamino group (e.g., m'ethylamino,ethylamino, propylamino, dimethylamino, diethylamino, dodecylamino,cyclohexylamino, flhydroxyethylamino, A di-B-hydroxyethylamino,fi-sulfoethylarru'no, etc.),- an arylamino group (e.g.', anilino, o, m-,and p-sulfoanilino, m-, and p-chloroanilino, o-, m-, and p-anisylamino,o-, m-, and p-toludino, o-, m-, and p-carboxyanilino, hydroxyanilino,sulfonaphthylamino, o-, m-, and p-aminoanilino, p-acetamidoanilino,etc.), etc., and R and R each represents a hydrogen atom or awater-solubilizing group, such as sulfo, carboxyl, etc. (as well asalkali metal or amine salts of such groups). Many of the compoundsrepresented by Formula II above are known substances, and methods forpreparing these compounds are well known. Listed below arerepresentative compounds selected from those represented by Formula II,although our invention is not limited in any sense to these particularcompounds. While the structural formulas are included for only the firstthree compounds, it is to be understood that the same numbering systemis employed throughout the specification.

(10) 4,4 bis[4 (2' chloroanilino') 6 hydroxystriazin-Z-ylamino]stilbene-2,2'-disulfonic acid (11) 4,4 bis[4 (5'sulfonaphthylamino) 6hydroxy-s-triazin-Z-ylamino]stilbene-2,2-disulfonic acid (12) 4,4 bis[4n dodecylamino 6 (,8 sulfoethylamino) -s-triazin-2-ylamino]stilbene-2,2'-disulfonic acid (13) 4,4 bis[4 N morpholinyl 6 (4'sulfoanilino) s triazin-2-ylamino] stilbene-2,2'-disulfon.ic acid (14)4,4 bis[4,6 di(N mor-pholinyl) s triazin 2- ylamino]stilbene-2,2-disulfonic acid (15) 4,4 bis {4 [4 (5" keto 3" methyl 2"-pyrazolin 1" yl) anilino] 6 hydroxy s triazin-2-ylanu'no}stilbene-2,2'-disulfonic acid (16) 4 [4 ethylamino 6 (di BhydroxyethyD- amino s triazin 2 ylamino] 4' [4 methylamino 6 8hydroxyethylamino) s triazin 2- ylamino] stilbene-2,2'-disulfonic acid(17) 4 [4 methylamino 6 8 hydroxyethylamino)- s triazin 2 ylamino] 4' [4ethylamino 6 (2'- anisidino) s triazin 2 ylamino] stilbene 2,2disulfonic acid (18) 4 [4 ethylamino 6 ([3 hydroxyethylamino)- N 1 Nno-cnioni-Nnf TNHGQEb-QHQNH-W fi-mnomom-on N N l N N NH-CHzCHz-OHlbene-2,2-disulfonie 8.01

4,4'-bis{4-[4'- N'-4"-sulfobenzyl-N'-ethyl) aminoanilino]-6-hydroxy-s-triazin2-y1amino}stiIbene-2,2-disulfonic acid (4) 4,4 bis[4(4 sulfoanilino) 6 3hydroxyethylamino-s-triazin-Z-ylamino]stilzene-2,2-disulfonic acid (5)4,4 bis[4,6 dianilino s triazinyl 2 ylamino]- stilbene-2,2'-disulfonicacid 6 (6) 4,4 bis [4 phenoxy 6 ([3 hydroxyethylamino)-s-triazin-Z-ylamino] stilbene-2,2'-disulfonic acid (7)4,4-bis(4,6-dianilino-s-triazin-Z-ylamino)stilbene (8) 4,4 bis(4,6dihydroxy s triazin 2 ylamino)- stilbene-2,2-disulfonic acid p (9) 4,4bis(4-anilino 6- hydroxy s triazin 2- ylamino) stilbene-2,2-disul.fonicacid (23) 4 [4 phenoxy 6 (,9 hydroxyethylarnino) striazin 2 ylamino] 4'[4 chloro 6 di(fi hydroxyethyl)amino s triazin 2 ylaminolstilbene-2,2'-disulfonic acid (24) 4,4 bis[4 ethylthio 6 (18hydroxyethylamino)-s-triazin-2-ylamino]stilbene-2,2-disulfonic acid (25)4,4 bis [4 phenyltbio 6 ([3 hydroxyethylamino) -s-triazin-2-ylainino]stilbene-2,2-disulfonic acid (26) 4,4 bis(s triazin 2 ylamino)stilbene2,2-

disulfonic acid (27) 4,4 bis(4 hydroxy 6 amino s triazin 2-ylamino)stilbene-2,2'-disulfonic acid (28) 4,4 bis(4 chloro 6trimethylolmethylaminos-triazin-Z-ylamino)stilbene-2,2-disulfonic acidCompounds of the above type which can advantageously be employed inpracticing our invention have been described in one or more of thefollowing representative patents:

2,171,427 Aug. 29, 1939 2,473,475 June 14, 1949 2,595,030 Apr. 29, 19522,660,578 Nov. 24, 1953 Br.:

I 595,065 Nov. 26, 1947 623,849 May 24, 1949 624,051 May 26, 1949624,052 May 26, 1949 678,291 Sept. 3, 1952 681,642 Oct. 29, 1952 705,406a Mar. 10, 1954 These products have been previously employed in thetextile field, and are sold under such tradenames as Leucophor B,Calcofluor White MR, Tinopal (SP, WR, BV277, 2B, GS, NG), Blancofor SC,Hilta'mine (BSP, N, 801., 6T6), and the like. l

According to our invention, we. incorporate onelor more of thedicarbocyanine dyes represented by Formula. I above with one or mores-triazinylam-inostilbene COIIL? pounds, such as those represented byFormula II above.

. Our invention is particularly directed to the ordinarily employedgelatino-silver-halide emulsions. However, our

. supersensitizing combinations can be employed in; silver halideemulsions in which the carrier is other than gelatin,

e.g., a resinous substance or c ellulosic material which has nodeteriorating effecton the light-sensitive materials. The dicarbocyaninedyes and js-triaziaylaminostilbene coated out on a suitable support,such as glass, cellulose derivative film, resin film, or paper, to asuitable thickcompounds can be employed in various concentrationsdepending upon the eifects desired.

Ordinarily, the optimum or near optimum concentration of thedicarbocyanine dyes which we employ in practicing our invention is ofthe order of from 0.010 to 0.30 g. per mol. of silver halide in theemulsion.

ness and allowed todry. The detail-s of such coating methods are wellknown to those skilled in the art. The

foregoing procedures and proportions are to be regarded onlyasillustrative. Clearly, our invention is directed to any silver halideemulsion containing a combination of the aforesaid dicarbocyanine dyesand s-triazinylaminostilbene compounds whereby a supersensitizing effectis obtained.

The s-triazinylaminostilbene compounds which we em, a ploy in ourinvention can advantageously be employed at I a concentration of fromabout 0.03 to 10.0 g. per mol. of silver halide in the emulsion.

In general, the ratio of concentration of dicarbocy- The followingexamples will serve to illustrate further the manner of practing ourinvention.

In Table I below, to different portions of the same batch ofphotographic gelatino-silver-halide emulsion were added (1) adicarbocyanine dye, such as those repanine dye s-triazinylaminostilbenecompound can varyv rather widely in our combinations, e.g., from 1:1 to1:300 (by weight) in many cases.

The methods of incorporating sensitizing dyes in silver halide emulsionsare well known to those skilled in the."

art. The s-triazinylaminostilbene compounds can be directly. dispersedin the emulsions, or they can be dissolved in water (or anorganicsolvent, such as methanol,

ethanol, etc., where the water-solubility is not sufiiciently.

great) and added inthe for-m oftheir solutions." While thedicarbocyanine dyes can be directly dispersed in the emulsions, it isconvenient to add the same in the form many of the dyes of 'Formula I.'.Mixtures of solvents, e.g., pyridine diluted with methanol or:acetone, can also be used. The dicarbocyanine dyes.ands-triaziny-laminostilbene compoundsa're dispersed in the. finishedemulsions and should be. uniformly distributed throughout the emulsions.The following procedure satisfac- "tory: Stock solutions of thedicarbocyanine dyes and stilbene compounds areprepared by dissolving thesame stilbene (in neutral aqueous solution).

of solutions in appropriate solvents; Methanol, ethanol, pyridine, andthe like have proven satisfactory for resented by Formula I above, and(2) a combination of the. dica'rbocyanine dye, and a bis(s-triaz-in-2-ylamino) Then the emulsions were held at about 40 C. fora short time and coated on a support, chill set, and dried. After expo:sure through a Wratten No. 25 filter, i.e., a filter whichtransmits'isubstantially no light of wavelength shorter than about. 580mu (Examples 1 to 14 and 17 to 31) or a Wratten.No. l2 filter, i.e., afilter which transmits sub-. .stantially no light of Wavelength shorterthan about 495 mu, (Examples and16) in an Eastman Type 13 sensitometer,the film strips were processed for 3 min.- utes in a developer havingthe following composition:

N-methyl-p-aminophenol sulfate g 2.0 Hydroquinone g 8.0 Sodium vsulfite(desiccated) g 90.0 'Sodiu'm carbonate (monohydrate) g 52.5 Potassiumbromide -1. g 5.0

Water to make 1 liter.

- The speed (red or minus blue), gamma and fog for each of the'coatingswas then measured. The results are recorded-inTable I.

I Table 1 Red or Minus Blue Light Exposure Example Sensltizlng Dye dzAddenda (g./m0l. AgX) 30/E Gamma Fog Speed 1 {(a)3,3-diethylselenadiearbocyaniue bromide (.075) 2. 3 .22 (b) dye (or)(.076) plus Oalcofluor White MR 1 (.13)- 2.0 .31 2 {(c)3,3-diethyloxathiadicarbocyanine iodide (050).... 3. 7 1. 3 .06 (d) dye(c) (.050) plus compound 4 (3.0) 20. 5 2. 7 .06 (e) dye 20) (.050) pluscompound 1 (3.0)- 6.7 2.4 .05 I) dye c) 050) plus compound 5 (3 0)- 24.5 2. 9 05 (a) dye (c) (050) plus comp und 6 (s.0) 22. 2. 9 .06 (h) dye(c) (.050) plus compound 2 (3.0) 27. 5 2. 8 06 (i) dye (a) (0375)...- 323.0 .06 (j) dye c) (.0375) plus compound 6 (2.5) 111 2.1 .06 {(lc) dye(c) (.050) nil nil .05 e (I) dye (c) (.050) plus Galcofluor White MR 1(3.0) 34.5 2.4 .06 (m) dye (a) (.050 5.1 .73 .07 (n) dye (a) (.050) plusOalcofluor White MR 1 (3.0) 16. 5 2.4 .06 (o) dye (c) (.050 4.65 1.5 .06(p) dye (c) (.050) plus Oalcofluor White MR 1 (3.0) 11.9 2.0 .06 {(q)dye (c) (.050) 4. 25 1.3 .06 (r) dye (c) (.050) plus Oalcofluor White MR1 (3.0) 13. 7 2. 3 07 (s) 3-ethyI-3'-B-hydroxyethyloxathiadicarbocyanineiodide (.050) 11.9 2. 8 06 t) dye (s) (.050) plus Calcofiuor White MR 1(3.0) 22.0 2. 3 07 u)3,3'-diethyl-fi-phenyloxathiadicarbocyanine-p-toluene-suL fonate (.050)I nil nil 06 a (0) dye (u) (.050) plus Calcofiuor White MR (3.0) 4.15 1. 3 .08

' Talile'I- -Contiriud v V Rodor Linu's Blue Light I xposure Examplesensitizing Dye & Addenda (gJmol. AgX) i 30/E Gamma -Fog Speed 14 (112%3-efililyl-ggg-hydroxyethyi-fi-phenyloxathiadicarbocyanlne 4 55 1 5 06ram 0 (z) dye (w) (.050) plus Calcofluor White MR 1 9. 25 1. 9 .08 (a)3'-diethy1oxadicarbocyanine iodide 050)."- 7. 7 2.0 .06 z dye 1) pluscompound 27 (.30) 19.0 2.1 .06 16 (a)0 33-diethyl-5,5-diphenyloxadicarbocyanine perchlorate 3 8 1 4 b6 0" dye (a.050 plus compound 21 91 1 21 1 I01 17 (0) 3.3-diethyl-fi7,6,7-dibenzoxadicarbocyanine iodide 050). 4. 2 1. 3 06 Ed) dye (0)(.050) plus compound 27 (.30 6.0 1.5 .07 18 e()03,3-d1methyl-4,5,4,5-dibenzothiadicarbocynnine chloride 93 79 06 (1')dye e .050) plus compound 21 1.1 1.4 I01 19 (0)3,3-diethyl-6,7,6,7-dibenzothladicarbocyanine iodide 2 6 '1 6 05 (11" do'f .050 pluseompound 21 414 111 I00 20 {(1')3,1-diethyl-5,6-benzoselena-2-dicarbocyanme iodide (.050). .97 .66 07(7) dye (1) (.050) plus compound 27 (.30) 3.3 1.9 .06 21 {(109053),3-diethyl4,5'-benzoselenathiadicarbocyanlne iodide 2 4 1 8 05 1') dye(7c .050 plus compound 21 (.30).........,.........: 310 .00 I00 22{(012%?,3-diethyl-6,7-benzoselenathiadicarbocyamne iodide 2 8 1 8 05 dye(131' (.050) plnscompound 21 3Z5 '.9 I00 23503,3-diethyli,5,6,7-dibenzothiadicarbocyanine iodide 1 6 1 2 06 (p do'i') .050 plus compound 21(.00) 01; 110 I00 24 (q') 3,1'-diethy1-67-benzothia-2-dicarbocyanlne iodide E ml nil 06 (r') dye (q) (.050) pluscompound 27 (.30). 3.9 1.6 .06 25 (s()0g,ldiethylifi,5,6-d1benzoth1a-2-d1carbocyanine iodide n ml 13 0 l1 (t) dye(0) (.050) plus compound 27 (.30) 4. 2 1. 1 .10 26 E116) (i),1-1i%t12628574;enzothia-i diigrlgzegamne iodide (050)-- in {1141: :1 ye u p uscompoun (w) 3,3-dlethyl-4,5,4,5-dibenzothiadicarhocyanineiodide 8.2 1.9.05 11.1 2.3 .06 2.2 1.4 .06. 3'? ii "6i 11 dye (c) .050) plus compound27 (.30) '8: 4 1: 9 v :07 31 {01200533'-diethy1-4,5,4,5'-dibenzose1enadicarbocyanine iodide 1 7 1 2 06 (1 dye(0) .050 plus compound 21 (.30); 414 2,10 100 1 =Calcofiuor White MR isa bis(a-triazin-2-ylamino)stilbene-zg -disulionic acid (assodiuni'salt).

In the above table, the coatings of Examples 2 to 6 were made from thesame batch of gelatino-silver-bromi odide emulsion, the coatings ofExample 1 were made from the same batch of gelatino-silverchlorobromideemulsion, the coatings of Example 7 were made from the same batch ofgelatino-silver-chlorobromide emulsion, the coatings of Examples 8 and 9were made from the same batch of gelatino-silver-bromiodide emulsion,the coatings of Example 10 were made from the same batch ofgelatino-silver-bromiodide emulsion, the coatings of Examples 11 to 14were made from the same batch of gelatino-silver-bromiodide emulsion,the coatings of Examples 15 and 16 were made from the same batch ofgelatino-silver-bromiodide emulsion, and the coatings of Examples 17 to31 were made from the same batch of gelatino-silver-bromiodide emulsion.No measments for the stilbene compounds alone are given in the table,since numerous coatings at the concentrations used in the table haveshown that these stilbene compounds when employed alone have no positivemeasureable cifect (sensitometrically).

Our invention is primarily directed to the ordinarily employedgelatino-silver-halide developing-out emulsions, e.g.,gelatino-silver-chloride, -chlorobrornide, -chloroiodide,-chlorobromiodide, -bromide and -bromiodide developing-out emulsions.Emulsions which form the latent image mostly inside the silver halidegrains, such as the emulsions set forth in U.S. Patent 2,456,956, datedDesupport, e.g., glass, cellulose nitrate film, cellulose ace-. 75

tate film, polyvinylacetal resin film, paper'or metal.

Photographic silver halide emulsions, such as those listed above,containing the supersensitizing combinations of our invention can alsocontainzs'uch addenda as chcmical sensiti'zers, e.g., sulfur sensitizers(e.g., allyl thio carbamide, thiour'ea, allyli'sothiocyanate, cystine,etc.), various gold compounds .(e.g., potassium chloroaurate, aurictrichloride, etc.) (see U.S. Patents 2,540,085; 2,597,856 and2,597,915), various palladium compounds, such as palladium chloride(U.S. 2,540,086), potassium chloropalladate (U.S. 2,598,079), etc., ormixtures of such sensitizers; anti-foggants, such as ammonium chloro-.platinateu(U.S. 2,566,245), ammonium chloroplatinite (U.S. 2,566,263),benzotriazole, nitrobenzimidazole, 5- nitroindazole, benzidine,mercaptans, etc. (see Mees The Theory of the Photographic Process,Macmillan Pub., page 460), or mixtures thereof; hardeners, such asformaldehyde (U.S. 1,763,533), chrome alum (U.S. 1,763,533), glyoxal(U.S. 1,870,354), dibromacrolein (Br. 406,750), etc.; color couplers,such as those described in U.S. Patent 2,423,730, Spence and CarrollU.S. Patent 2,640,776, etc.; or mixtures of such addenda. Dispersingagents for color couplers, such as those set forth in U.S. Patents2,322,027 and 2,304,940, can also be employed in the above-describedemulsions.

Such silver halide emulsions can also contain thiazolidones or otherultraviolet absorbing compounds, such as those described in thecopending application Serial No. 419,239, filed March 29, 1954 in thename of G. W. Sawdey, now U.S. Patent 2,739,888, issued March 27, 1956.While certain emulsion addenda, such as certain ultraviolet compounds,and certain color-forming compounds cause de-sensitization orun-sensitizing efifects, it has been found that the'new combinations ofour invention largely overcome such effects. Typical color-form- 'Q ingcompounds which can be so employed include those in U.S. Patent2,322,027 and the following:

Coupler: v 1

(1) 1-hydroXy-2-[6-(2',4 di tert.-amylphenoxy)- n-butyll-naphthamide(U.S. Patent 2,474,293)

(2) l-hydroxy 4 pl1enylazo-4-(p-tert.-butylphenoxy) -3-naphthanilide(U.S. Patent 2,521,903)

(3) 2-(2,4-di-tert.amylphenoxyacetamino) 4,6-dichloro-S-methyl phenol(Graham U.S. application Serial No. 285,544, now U.S. Patent 2,725,291)

(4.) 2-(oz-2,4-di-EOIL8Il'lYlPhen0XY n-butyry-lamino)-4,6-dicl11oro-5-methyl phenol i t (5) 6-{a-{4-[ t-(2A di tert.amylphenoxy)butyra amido] -'phenoxy}acetamido}-2,4 dichl'oro 3 methylphenol a V (6) 2-[3 (2",4" diamylphenoxy) acetamidolbenzamido-4-chloro-5rnethyl'phenol (7) 1-(2',4',6'-trichlorophenyl)-3-[3" (2"',4"'ditert.-amylphenoxyacetamido) benzamidol-5-pyrazolone (U.S. Patent2,600,788)

(8) 1-(2,4',6';trichlorophenyl)-3 [3"4 2"',4-ditertamylphenoxyacetamido)benzamidol-4-(pmethoxyphenylazo)-5pyrazolone c i (9)N-(4-benzoylacetaminobenzenesulfonyl)7- N-(y- V phenylpropyl)p-toluidine (U.S. Patent 2,298,443) (10) a-o-Methoxybenzoyl g onChlOfCi-4 [oc-( 2,4 -di now U.Si Patent 2,728,658,1Eissued"Decernber 27,'1

11 Mata- 2,4 di tert garnylphenoiiy) acetami do]-benzoyl}-2-methoxyacetanilide amylphenoxyacetanili'de V -(13-)4-benzoylacetarnido 3 j-1methoxy -2;,'4-di-jtert.-jamylphenoxyacetanilide The following examples will serve to illustrate the Theresults follow:

7 Red Speed Minus Blue Speed 7 dye (c) alone .81 .86 dye (a) plusLeucophor B. 2. 29 v The coatings describedin the following exampleswere prepared in substantially the same manner as those set forth inExample 3.2- above. However, no ultraviolet absorbing compound wasemployed and the emulsions werecoated on a cellulose acetatesup'portinstead of paper.

(both, 10 g./n'1ol. AgX) wasemployed as shown in Table 11 below.. Tomeasure' the anti-unsensitizing efiect Either Leucophor B or CalcofluorWhite MR 7 I j jof these stilbene compounds, series of coatings wereheld tert. amylphenoxy) n-buty-ramido] aetanilide '(McCrossen US.application Serial; No'. -295,806; l

beneficial effects of our new supersensit'iz-ing combinations I whenemployed in multilayer photographic emu'lsio'n layerscontaining'inc'orporated color-forming" compounds,

7 fE XAMPLEBZ. I p v A photographic gelatino-silver1chlorobromideemulsion containing a coupler dispersion of aeoloriforniingf compound,Such as coupler No. 5 above, anda vthjajz'olidorle ultraviolet absorbingcompound, such;as Sabenzal-d-ncetyl-2-phenylirnino 4-thiazolid0ne,v was;sensitized ,With

tion of such sensitized emulsion added Leucophor B coated paper supportsand the. coatings exposed on a sensitometer and reversal processed byfirst developing for 6 minutes in a developer having the followingcompo- Water to make 1 liter. 7

After treatment in a conventional stop bath and washn the coatingswerere-exposed with a photoflood and color developed in a bath of thefollowing composition:

sition:

. G. Calgon (sodium hexameitaphosphate) ,..2 .04-.N-methylaminophenolsulfate Hydroquinone 2.35 Sodium sulfite (anhyd8.0 Sodium carbonate (anhyd) 10.0 Potassium bromide Q ;.Q .55Sodiumchloride n v j .20' S-methylbenzcitriazole 1.02

' Water (70-75711) at 40 C. for-30 minutes and 60 minutes, respectively,1

before coating for comparisonwitha series offresh coat ings (0 holding).Theflcoatings'were thenexposed in the usual manner sms color developedinfa developer having the following composition:

aminq-s-si inyla mb toluene hydrochloride. .1

The coating wa s then rinsed, fixed, bleached with potassiumdichrornate, 'etc., in the usual manner. MT he results are given in' thefollowingtable, 5 1 v 5 Table. 11 1 j 'Red Minus Example Addenda HoldingTime Speed 'Blue V V Speed neiie-.- i- 4L.-. 1111 .so LeucophorB 1.11.87 Calcofiuor W111 e MR..- 0 1.30 none. nil .83 1 Leueophor B .62 .88Oalcofiuor White MR; .98 I 81 none 6O @40 nil .86 Leucophor B 6 .44 .91Oalcofluor White MR 60@40 C .69 .70

In exactlyjthe manner described for the coating of Table I, dye' (c)(.050 :g./m0l. AgX) was incorporated in an ordinarygelatino-silver-bromiodide emulsion and together (at the-sameconcentration) with'compound 7 (8.0 g./mol. AgX). The relative speed(red), gamma and fog are given for each of these coatings;

; 'Exampleat) Relative Gamma Fog t Speed dye(c)lalone 4.5 I .06 dye (0)plus compound 7.. 245 5.3 .06

While we have found thattricarbocyanine dyes corresponding to thedicarbocyanine dyes of Formula I (e.g.', 3,3'-diethylthiatricarbocyanineiodide) can sometimes be used to advantage in combination with the com-The relative red ,andminus blue speeds (density 0.3 fog) for'each of thecoatings was measured.

provide as advantageous results as those described above. A set ofcoatings of an ordinary gelatino silver-bromiodide emulsion was preparedas describedabove for the coatings of Table I. The results follows:

In Examples 40 and 41, the amounts are given as g./mol. A'gX.

The dicarbocyanine dyes of Formula I above comprise a well known cl assof optical sensitizing dyes. Methods for making these dyes have beenpreviously de scribed in the prior art. See, for example, US. Patent2,131,865, issued October 4, 1938; US. Patent 2,213,238,

, issued September 3, 1940; US. Patent 2,218,450, issued EXAMPLE 443,3'-diethyl-5-phenyloxathiadicarbocyanine p-toluenesulfonate rHs C1415A mixture of 3.49 g. '(1 mol.) of 3-ethyl-2-methylbenzothiazoliump-toluenesulfonate, 4.77 g. (1 mol.) of 3-ethyl-2-(4-methoxy 1,3butadienyl) 5 phenylbenzoxazolium p-toluenesulfonate and 2.02 g. (1 mol.plus 100% excess) of triethylamine in 35 ml. of absolute ethyl alcoholwas stirred at room temperature for 5 minutes. After chilling thereaction mixture, it was filtered and the residue was washed with ethylalcohol. The yield of dye was 100% crude and 74% after tworecrystallizations :from methyl alcohol. .The green. needles melted at221-222 C. with decomposition.

. The 3-ethyl-2-(4-meth'oxy-1,3-butadienyl) 5 phenylbenzox-azoliump-toluenesulfonate was prepared as follows. The crude quaternary saltobtained by heating 99.5 g. of Z-rnethyl-5-phenylbenzoxazole and 100 g.of ethyl p-toluenesulfonate together overnight at 110 C.

' was dissolved in 500 ml. of acetic acid. Them 132 g.

October 15, 1940; US. Patent 2,269,234, issued January 6, 1942; andBritish 562,567, accepted July 6, 1944. The

following examples will serve to illustrate these well known methods.

, EXAMPLE 42 3,3I-diethyl 5,5'-diphenyloxadicarbocydfzirte perchlorate Amixture of 3.65 g. (2 mols.) of 3-ethyl-2-methyl-5- phenylbenzoxazoliumiodide and 1.74 g. (1 mol. plus 100% excess) of 1,3,3-triethoxypropenein. 10 mlfiof acetic anhydride was heated, with shaking; atthe.refluxing temperature for about Sfminutes. The coolreaction mixturewas stirred with ether, the liquors Weredecanted and the remainingresidue was stirred with hot acetone. After chilling, the solid wascollectedon afilter and washed with acetone andthen water.. Afteronerecrys-v tallization from methyl alcohol the dye was converted to theperchlorateby adding a hot aqueous solution of sodium perchlorate to ahot methyl alcoholic solution of the dye. The dye was recrystallizedfrom methyl'alcohol. The coppery crystals melted at 2 34-236 C. withdecomposition. EMMPLE 433-ethyl-3'-B-hydroxyetiiyloxaihiadicdrbocyaniite iodide 7 A mixture of5.48 g. (1 mol.) of 3-fi-liydroxyethyl-2- methylbenzothiazolium bromide,7.14 g. (1 mol.) of 3 ethyl-2-(4-methoxy-1,3 butadienyl)benzoxazoliumiodide and 4.04 g. (1 mol. plus 100% excess) oftri'ethylamine in 50 ml.of absolute ethyl alcohol was stirred at room temperature for 5.minutes. The reaction mixture was filtered and the residue wasthoroughly washed with water and then with a' little methyl "alcohol.The yield of dye was 53% crude and 35% after two recrystallizations frommethyl alcohol. The green crystals melted at 250-25l C. withdecomposition.

of 1,3,3-,tr i methoxypropene was added and the reaction mixture washeated at the refluxing temperature for 30 minutes. After chilling, withstirring, the intermediate was collected on a-filter and washed firstwith ether and then with acetone. 'The yield was 74 g.

EXAMPLE .,3-ethyl-3' fi hydroxyethyl-5-phenyloxathiadicarbocyaninebromide zHa Br CHzCHrOH A' hot solution of 2.75 .g. (1 mol). of3-fi-hydroxyethyl-Z-methylbenzothiazolium bromide in ml. of absoluteethyl -alcohol-was cooled quickly with stirring" to room temperature.Then 4.77 g. (1 mol.) of 3-ethyl-2- gmon omon-omcn-o CGHB- V I p i v I(4 methox'y-1,3-butadienyl) 5 phenylbenzoxazoliumptoluenesulfonate-and"2.02 g'. (1 mol. plus excess) of triethylaminewere added and the reaction mixture was stirred at room temperature for10 minutes. The dye'wascollected on a filter and Washed with methylalcohol.- The yield offdye was 77% crude and 49% after tworecrystallizations from methyl alcohol. The blue needles with a greenreflex melted at 255-256 C. with decomposition.

Listed below are the melting points of dyes used in the above tables,which were prepared in exactly the samemanner illustrated in Examples43-46 above.

Dye: Melting point y .'229-230 C. with decomposition. e' 215-216 C. withdecomposition. g" 236-237 C. with decomposition. i" 178-l80 C. withdecomposition. k l77178 C. With decomposition. .me 220-221 C. withdecomposition.

0' F 186-187 C. with decomposition. q 189-191 C. with decomposition andshrinking from about 180 C. s, 208209 C. with decomposition. u 191-195C. with decomposition and shrinking from about C. c" 225-227? C. withdecomposition. e" 215-216" C. with decomposition.

P u ds repr sentedwby. .linnu V senses of UIS. Patent 2 ,269,23 4 (usingiiitermedia te-ofEXaniple 1 and the benzimidazole quaternar "salt'sjofU.S. patent 1t me tedat 1497 .55? ,C-' 0 po 'As noted about the, 2

known class of ffoptica ;--.;b1eachin g: agents} and methods; for,making them, he

reference: tethepreflaration of'tcompound 9 above,

Step 1.-Three solutions were-prepared as followsz (a) 260 g. of''purified 'diamino stilbene;'disulfonic acid 7 in 1 liter of water.

, Step 2. To this reactionproduct was added separate solutionsfid) and(e) as shown below. at 0-10 C.

fne was present-.2

Step .i'Q-Added 550 m1. of IS percent sodium care bonate solution to thereaction mixture from Step 2. Heatedtoboiling and the acetonedistilledifofil :I-Ieated several hours-afterthe-acetonewas removed anddiluted outwashing. The optieaL-bleachconcentrateiwa's then dried at70'-80* G; and was -in--the following: chemical fdi'im In "a*similarzmannei compound 2;? waslprepared as above, using concentratedammonia in place of the ani- '75 at concentrations of 1 gram'of compoundper mole of rnp r ise a well i been fully describedi th p j artlistedabove-W'fm can e v a i rthe t m-2 ters of Water "line usednialiingtcompound 9 Likewise, compound 28 was made by employing tris(hydroxymethyl) aminoinethane'in place of aniline (no Step 3 was used)Corn? pa m "2 6w'as prepared by a condensation similar to Step 1 whereincompound 9 was prepared, followedby rednotionv oi the resultingtetrachloro compound to give acofiipound'whei'ein R R3, R6 IId"R7 ofFormula II is hydrbgen by heating with a'zinc-acetic acidreductionjmixlj Compound 7 was preparedexactly as 'com- 7 pound (US;2,582,357) by using 4',4'-diaminostilbene in 'pla'ce offlthecorresponding stilbene disulfonic acid useful in practicing ourinvention are compounds represented by Formula II above wherein R R Rand/ i 1 (gr- R each represents a heterocyclylamino group (e.g.,

herewith.

- of the type described above to prevent or diminish the 'f imilfign' ofspontaneous fog which develops upon exe of'the" emulsions to hightemperatures and hu- H Alsop we l iave found that the compounds ofFormula-.I-I rhave the valuable property of inhibiting the formation of-.stain which frequently remains'after proc- "s teen-2516.- and I essingof photographic emulsions containing color-forming compounds.iTheantifoggant and/ or antistain action of'theicompounfis of Formula 11appears to be unrelated" tothe supers'ensi'tizing eifect shown in theabove examples.

That"is,'this antifoggant or antistain action appears to fomjpm'ir dvt/a s present: take place regardlessof the presence of sensitizing dyesNn-h iinncini in, the photographic-emulsions containing the color-form-1 standing in the presence of color-forming compounds for the magenta orcyan images, i.e., in the presence of magenta jor cyan couplers (e.g.,such as the magenta and ,cyan couplers described in US. Patent 2,640,776mentioned. above) The antifoggant and antistain action \2 V v(compoundQ) oi the compounds of Formula II is particularly apparent 15silver halide or amounts in excess of 1 gram (e.g., from about 1 tograms per mole of silver halide). It has been also found that thecompounds of Formula-II are, particularly useful in combination withcolor couplers of the water-soluble type (suchas the couplers describedin US. application Serial No. 470,499, filed November 22, 1954, nowU.-S.-Patent No. 2,808,329, granted Octoher 1, 1957). Such couplers whenused in the absence of the compounds of Formula II cause suflicientlyhigh fog to make their use difficult in photographic emulsions. However,when using such couplers'in the presence of the compounds of Formula II,the fog is reduced to a considerable degree so that such couplers canbe'employed from a practical standpoint.- a The following examples willserve to illustrate the antifoggant and antistaining action of thecompoundsof. Formula II when employed in photographic" silver halideemulsions containing color-forming compounds.

were

the times shown in the table before exposure. vThe exposed'coatings werethen processed in a color developer havin'gthe following composition:

' Benzyl alcohol 3.8 Calgon l *3 '2.0 Sodium sulfite (anhydrous) ..g 2.0Sodium hydroxide (cold 10% solution) cc 5.5 Developer 1 I g 5.0

-' Potassium bromide g 1.0 Sodium carbonate monohydrate g 50.0

EXAMPLE 46 A photographic gelatino-silver-chlorobromide emulsion whichhad been optically sensitized with one of the dyes of the typerepresented by Formula I above and containing a coupler dispersion of acolor-forming compound, such as coupler No. 5 above, was coated on acellulose acetate film support. Separate batches of the same emulsionwere prepared and to these batches were added'Calcofluor White in theamounts given below, and these emulsions were also coated on celluloseacetate film supports. Separate portions of the coatings were thenexposed both before and after incubation at 120 F. for seven days,

50 percent relative humidity, through a Wratten No. 5 Filter (Le, afilter which transmits substantially no light shorter than 580 mu.) anda Wratten No. 47 Filter (i.e., a filter which transmits only lightbetween about 355-515 mu). Thecoatings were then developed in a colordeveloper, such as that described for Examples 33 to 38' above.Processing was completed in the same manner described for Examples 33 to38. The speed figures given below for the coatings are for log E valueswhere the log E is measured at a point on the curve where the density is0.2- above' fog. The speed shifts on incubation given in the table weremeasured as A log E. The results which were obtained are as follows:

. Separate portions of a negative speed gelatino-silverbromiodideemulsion weregreen sensitized according to the method described in US.Patent 2,701,198 or US. Patent 2,165,338 (or by a mixture of the dyesshown in these patents). A mixture of couplers, such as couplers Nos. 7and 8 above, was then added to the emulsions. To certain portions of theemulsions was added a compound of Formula II in the amount given in thetable below. 'The emulsions were then coated on cellulose acetatesupports and one group of fresh coatings was exposed on an intensityscale sensitometer through a Wratten No. 58 Filter, Le, a filter whichtransmits only' light of wavelengths lying-between 465 and 620 mu. Theremaining Water to make 1 liter.

1 e-amino N ethyl N S' methanes'ulfonamidoethyh-m toluidinesesquisulfate monohydrate.

are as follows:

Original Tests Incubation Tests Addenda Coating (gJmOLAgX) Speed FogTime, Speed Fog Days Shift (0) Control- .17 7 ..14 .33 (b) Galcofiuor 14.10. 7 .10 .11 A White 5.0). (0) Control. .15 28 .16 .25 (d) Calcofiuor.15 .08 28 .19 .09

White (5.0).

EXAMPLE 4s- To separate portions of a negative speedgelatino-silverbromiodide emulsion of the type normally used in reversalcolor films was addedan optical sensitizing dye of the typeshown in US.Patent 2,165,338inthe amounts shown in the table below. To each portionof this emblsion was added a v dispersion ofa color eoupler, such' ascoupler No. 7 above. To certain portions of the emulsion was added the.compound of Formula 11, in the amounts shown in the table. One group ofthe coatings was then exposed in an intensity scale sensitometer inexactly the manner described in Example 47 above, while the other groupof coatings was incubated for 7 days at 120 F.,

50% relative humidity before exposure. The exposed Example 32 above andthen in a color coatings were then reversal processed, first in aconventional black and white developer, such as that shown in developerhaving the following composition: j I

' 1 4-amino N ethyl N (B methanesulfonamidoethyl)m- I toluidine.sesquisulfate monohydrate;

f The developed coating was then bleached in a conventional potassiumdichromate-potassium ferricyanide bleach. The speed and density for eachof the coatings coatings as identified in the table, wereincubated forwas then measured. 'The speed figures givenin the table gawk . 17 beloware expressed as IO/log where log'Efisjmeasured at a density of 0.3below D-rnax. The results fono'w:

118i "100 -F., 50% relative humidityQ'IfheemuI sionS were then exposedexactly as described in Example 46 above,

To separate portions of a gelatino-silver-bromiodide emulsion whichhadbeen green sensitized with a dye of the type described in US. Patent2,241,237 or 2,165,338

(or a mixture of such dyes) were added coupling comand "processed asdescribed in Example 46. The dicarbocyanine dye used in this example wasof the type described in U. S. Patent'2,213,'23 8, while the merocyaninedye was of the type described in US. Patent 2,282,116. The resultsobtained Wereas follows:

- 'Coatlngnae I.

pounds of the type indicated in the following table. .To certainportions of the emulsions was added a compound of Formula II in theamounts indicated in the table. The emulsions were then'coatedoncellulose acetate supports and exposed in an intensity scalesensi'torneter as described in Example 47 above. The exposeden'iul'sionswere then processed in exactly the same manner shown in Example 47. Theresults obtained are illustrated in the following table:

14= 1 -phenyl-3- (2- earboxybenzamido) A do dec y loxyphenylazo)pyrazolone.

EXAMPLE 50 To separate portions "of a positive"speedigelatino-silverchlorobromide emulsion was added a color couplenspch as coupler No. 5 above. "Tosome of these portions'was added anoptical sensitizing .dyefas indicated in the table below, as well as'acompound bfFor'rruila The'emulsions were then coated on a conventionalcellulose acetate support. Some of the emulsions were-exposedimmediately after coating and drying, while some of the emulsions wereexposed only'afteriincubation, as set forth in the table. Thecoat'ingsincubatedfor 7days were exposed to a temperature of 120 F., 50% relativehumidity,

- while the coatings incubated for 28"days were hld at Incubation Testsv a Fresh Tests,

r LogEShitts r c Addenda'(g.lmo1.- AgX) Y i ALog-E Shifts 1 Time, StainDays Shift Red Minus Red Minus B e Blue 7 +.30. +.04 Leucophor'B (10.0)7 +.24 +.02 Calcofluor White (10.0) 7 22 00 none 7 +.06 +.26' +.04Leucophor B (10;0) p 7 +.06 +.00 +.02

The accompanying drawings illustratesthe supersensitizing efiectobtained with three of our new combinations ingelatino-silver-bromiodide emulsions. Each figlire in the drawing is adiagrammatic reproduction of one 'or' two v(Fig. 1) spectrogram's. ,Thesensitivity ofthe emulsion containing only the dicaibocyanine dyerepresented by Formula I is represented by the broken line in Fig'. 1,while the sensitivity of the "same emulsion containing both adicarbocyanine dye of Formula I and the triazine compound of FormulaIIis represented by the I solidcurve. No curve for the emulsion containingthe triazine compound *of Formula II alone is given, since it has beenfound that these compounds alone'generally have little or norne'sureable sensitizing 'fiect on the 'emulsions. The same sensitizingdye was employed-in the coatings of Fig, 2 and Fig. 3 as was used inFig. 1', hence curve A off'Eig; 1 (is not reproduced in Figs. 2 and 3'sin ce it vvoiild. merely be identical thereto. "In Fig. 1-,cu1 ve"Arepresents the sensitivity'of an ordinaryge1atino-silver-bromiodideemulsion containing 3,3- diethyloxathiadicarbocyanine iodide, whilecurve B represents the sensitivity ofthe same emulsion sensitized with3,3' diethyloxathiadicarbocyanine iodide and 4,4-bis[4- i( l'sulfoanilino) -6-l3-hydroxyethylarnino-s triazin 2 ylamino]stilbene-2,2'-disulfonic acid. 7 V I In Fig. 2, curve C represents thesensitivityof ordinary gelatino-silver-bromiodide emulsion sensitizedwith 3,3-diethyloxathiadicarbocyanine iodide and 4,4f-bis(4,6- dianilinos;triazin-2 ylamino stilbene; -2,2-disulfonic acid.

In Fig. 3,curve D represents the sensitivity of an ordinary gelatinosilver-bromiodide emulsion sensitized with3,3"-diethylokathiadicarbocyanine iodide and 4,-'4 -bis, ('4- V phenoxy6 8-hydroxyethylamino-s-triazin 2 -ylami no) stilbene 2',2'-disulfonicacid. 'The sensitor'netrioj measurem'ents for the coatings of Figs; 1, 2and 3are given in EXampI es Z; 4am 5 of Table "I above.

By bis(s-triazin-2-ylamino)stilbene compound; we

. mean acompound of the followiug structure:

- D-N H NH-Dr wherein R and R each have the values given above, and

D and D each represents a s-triazin-2-yl nucleus.

The disulfonic acids of Formula II are generally em-- ployed in neutralaqueous solution as mentionedabove, i.e., the free acids are at leastpartially neutralized with;

sodium hydroxide, potassium hydroxide, sodium carbon desire securedfollowing general formula:

' taining not more than four carbon atoms, n represents a groupconsisting of those of the benzothiazole series, those of thenaphthothiazole series, those of the benzoxazole series, those of thenaphthoxazole series, those of the benzoselenazole series, and those ofthe naphthoselenazole series, and Z represents the non-metallic atomsnecessary to complete a heterocyclic nucleus selected. from the groupconsisting of those of the naphthothiazole series, those of thebenzoxazole series, those of the naphthoxazole series, those of thebenzoselenazole series, those of the naphthoselenazole series, those ofthe 2-quinoline series, those of the 4-quinoline series, those positiveinteger of from 1 to; 2, X represents an acid radical, Z represents thenon-metallic atoms necessary to complete a heterocyclic nucleus selectedfrom the group consisting of those of the benzothiazole series, those ofthe naphthothiazole series, those of the 'benzoxazole series, those ofthe naphthoxazole series, those of the benzoselenazole series, and thoseof the naphthoselenazole series, and Z represents the non-metallic atomsnecessary to complete a heterocyclic nucleus selected from the groupconsisting of those of the naphthothiazole series, those of the'benzoxazole series, those of the naphthoxazole series, those of thebenzoselenazole series,

those of the naphthoselenazole series, those of the. 2-

quinoline series, those of the 4-quinoline series, those of thebenzimidazole series, and those of the 5,6-benzoquinoline series, and atleast one bis(s-triazin-2-ylamino)- stilbene selected from the classrepresented by the following general formula:

carbocyanine dye selected from the class represented by the followinggeneral formula:

h I R"N(- GH=CH)n'l'-'C=CH-CH=CH-CH=CH6=IFRI X wherein R and R eachrepresents an alkyl group contamlng not more than four carbon atoms, 12represents a positive integer of from 1 to 2, X represents an acidradical, Z represents the non-metallic atoms necessary of thebenzimidazole series, and those of the 5,6-benzoquinoline series, and atleast one bis(s-triazin-2-ylamino)- stilbene selected from the classrepresented by the following general formula:

wherein D and D each represents a s-triazin-2-y1 nucleus. 3. Aphotographic gelatino-silver-bromiodide emulsion sensitized with asupersensitizing combination of at least one dicarbocyanine dye selectedfrom the class represented by the following general formula:

wherein R and R each represents an alkyl group containing from 1 to 2carbon atoms, n represents a positive integer of from 1 to 2, Xrepresents an acid radical, Z represents the non-metallic atomsnecessary to complete a heterocyclic nucleus selected from the groupconsisting of those of the'benzothiazole series, those of thenaphthothiazole series, those of the benzoxazole series, those of thenaphthoxazole series, those of the benzoselenazole series, and those ofthe naphthoselenazole series, and Z represents the nonmetallic atomsnecessary to complete heterocyclic nucleus selected from the groupconsisting of those of the naphtothiazole series, those of thebenzoxazole series, those of the naphthoxazole series, those of thebenzoselenazole series, those of the naphthoselenazole series, those ofthe Z-quinoline series, those of the 4-quinoline series, those of thebenzimidazole series, and those of the 5,6-benzoquinoline series, and atleast one bis(s-triazin-2-ylamino)-stilbene selected from the classrepresented by the following general formula:

wherein D and D, each represents a s-tliazin-Z-yl nucleus.

4. A photographic gelatino-silver-chlorobromide emulsion sensitized witha supersensitizing combination of at least one dicarbocyanine dyeselected from the class represented by the following general formula:

wherein R and R each represent an alkyl group containing from 1 to 2carbon atoms, 11 represents a positive integer of from 1 to 2, Xrepresents an acid radical,

Z represents the non-metallic atoms necessary to complete a heterocyclicnucleus selected from the group consisting 'of those of thebenzothiazole series, those of the naphthoing of those of thenaphthothiazole series, those of the benzoxazole series, those of thenapthoxazole series, those to complete a heterocyclic nucleus selectedfrom the '(Q 9; Pgnzoselcnagole series, those of the naphthoselencasterazo le series, -tho's'e of the 2 -quinoline serienthose of the4-quinoline series, 'those ofzthe benzimidazole series, and

.those of .the 5,-6-benzoquinoline series,-and at least onebis(s-triazin 2-ylamino)-stilbene selected from the class v representedthe following general formula:

wherein R and R each represents an alkyl group containing from 1 to 2carbon atoms, X represents an acid radical, Z represents thenon-metallic atoms necessary to complete a heterocyclic nucleus of thebenzothiazole series and Z represents thenon-metallic atoms necessary tocomplete a heterocyclic nucleus of the benzoxazole series, and at leastone bis(s-triazin-2-ylamino)- stilbene compound selected from the classrepresented by the following general formula:

wherein D and D each represents a s-triazin-Z-yl nucleus.

6. A photographic gelatino-silver-halide developing-out emulsionsensitized with a supersensitizing combination of3,3'-diethyloxathiadicarbocyanine iodide and at least onebis(s-triazin-2-ylamino)stilbene compound selected from the classrepresented by the following general formula:

wherein D and D each represents a s-triazin-Z-yl nucleus.

7. A photographic gelatino-silver-halide developing-out emulsionsensitized with a supersensitizing combination af3,3-diethyloxathiadicarbocyanine iodide and 4,4-bis-(4,6-dianilino-s-triazin 2. ylamino)stilbene2,2-disu1- fonic acid.

8. A photographic gelatino-silver-halide developing-out emulsionsensitized with a supersensitizing combination of3,3-diethyloxathiadicarbocyanine iodide and 4,4'-bis-(4,6-di-fl-hydroxyethylamino striazin-2-ylamino)-stilbene-2,2-disulfonic acid.

9. A photographic gelatino-silver-halide developing-out emulsionsensitized with a supersensitizing combination of3,3'-diethyloxathiadicarbocyanine iodide and 4,4'-bis- (4-phenoxy 6 flhydroxyethylamino s triazin-Z- ylamino) stilbene-2,2'-clisulfonic acid.

10*. A photographic gelatino-silver-halide developingoutemulsionsensitized with a supersensitizing combination of a dicarbocyanine dyeselected from'the class represented by the following general formula:

wherein R and R each represents an alkyl group containing from 1 to 2carbon atoms, X represents an acid radical, Z represents thenon-metallic atoms necessary to complete a heterocyclic nucleus of thebenzothiazole series and Z represents the non-metallic. atoms necessaryto complete a heterocyclic nucleus of the benzimidazole series, and atleast one bis (s-triazin-2-ylamino)- stilbene cofiip'ound selected "fromtaverns represented by the following general formula:

wherein D and D each represents a s-t'riazin-2-yl nucleus.

11. A photographic gelatino-silver-halide developingont emulsionsensitized with a supersensitizing combination of(3-ethyl-2-benzothiazole)(3ethyl-l,7-trimethylene-Z-berlzimidaiole)pentamethincyanine iodide, andat least one b'is(s-triaz in'-2-ylainino) stilbene compound selectedfrom the'class represented by the following gen- 'eralformul'a:

wherein R and R each represents an alkyl group containing from 1 to 2carbon atoms, X represents an acid radical, and Z represents thenon-metallic atoms necessary to complete a heterocyclic nucleus of thebenzoxazole series, and at least one bis(s-triazin-2-lyamino)stilbenecompound selected from the class represented by the following generalformula:

wherein D and D each represents a s-triazin-Z-yl nucleus.

14. A photographic gelatino-silver-halide developingout emulsionsensitized with a supersensitizing combination of3,3'-diethylomadioarbocyanine iodide, and at least onebis(s-triazin-2-ylamino)stilbene compound selected from the classrepresented by the following general formula:

| 80311 BOIH wherein D and D each represents a. s-triazin-Z-yl nucleus15 A photographic gelatino-silver-halide developingout emulsionsensitized with a supersensitizing combination of3,3-diethyloxadicarbocyanine iodide and 4,4-bis-(4-hydroxy-6-amino-s-triazin-2 -ylamino)stilbene 2,2- disulfonic acid.

16. A photographic silver emulsion capable of producing a dye imagecomprising a photographic silver halide emulsion containing (1) adispersion of a color-forming compound selected from the groupconsisting of (a) a phenol compound capable of coupling with theoxidation products of a primary aromatic amine developing agent toprovide a cyan image and (b) a pyrazolone compound capable of couplingwith the oxidation products of a primary aromatic amine developing agentto provide a magenta dye image, and. (2) a bis(s-tri azin-2-ylamino)-enema by the following general formula:

wherein R R R and R each represents a member selected from the groupconsisting of a hydrogen atom, a hydroxyl group, an aryloxyl group, analkoxyl group, a halogen atom, a heteroeyclieradieal, an alkylthiogroup, an arylthio group and an amino group, and R and R each representsa mernber selected from the group consisting of a hydrogen atom and asulfo group, said bis- (stria zin-2-ylamino)stilbene compound beingincapable of coupling with/the oxidation products of a primary aromaticamine developing agent to provide a dye image.

References Cited, in the file of this patent UNITED STATES'PATENTS VCarroll Feb. 3, 1942 2,367,551 Yule 'Jan. 16, 1945 2,397,867 JenningsApr. 2,1946 2,418,747 Bailey .5; ---.Apr., 8, 1947 2,476,536" Ders chJuly 19', 1949 2,701,198 Carroll Feb. 1, 1955 2,718,466 Wolfson Sept.20, 19 55 'FOREIGN PATENTS 675,656 Great Britain Iuly16, 1952 878,823Frnee' Nov. 2, 1942 OTHER REFERENCES Mees: The Theory of thePhotographic Process," MacMillan Co., N.Y., 1954, page 365.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 2, 945,762

July 19, 1960 Burt H. Carroll et al.

Column 3, line 66, for "stilzene" read stilbene column 5, line 28, after"dye" insert to column 10, line 10, after "0.3" insert above column 11,line 4L for "follows" read follow column 13, lines 46 to 55, Step 2 theleft-hand portion of the formula should appear as shown below instead ofas in the patent:

I C I-l HN-C\ C-NH- column 18, {Line 40, for "drawings" read drawingline 53, for "mesureable" read measurable column 2O line 40, after"complete" insert a line 62, for "represent" read represents column 21,line 47, for "af" read of column 22, line 39 for "lyamino)" readylamino) Signed and sealed this 18th daybf April 1961. (SEAL) I Attest:

ERNEST w-imswmER DAVID L. LADD Attest'ing Oflicer Commissioner ofPatents

16. A PHOTOGRAPHIC SILVER EMULSION CAPABLE OF PRODUCING A DYE IMAGECOMPRISING A PHOTOGRAPHIC SILVER HALIDE EMULSION CONTAINING (1) ADISPERSION OF A COLOR-FORMING COMPOUND SELECTED FROM THE GROUPCONSISTING OF (A) A PHENOL COMPOUND CAPABLE OF COUPLING WITH THEOXIDATION PRODUCTS OF A PRIMARY AROMATIC AMINE DEVELOPING AGENT TOPROVIDE A CYAN IMAGE AND (B) A PYRAZOLONE COMPOUND CAPABLE OF COUPLINGWITH THE OXIDATION PRODUCTS OF A PRIMARY AROMATIC AMINE DEVELOPING AGENTTO PROVIDE A MAGENA DYE IMAGE, AND (2) ABIS(S-TRIAZIN-2-YLAMINO)STILBENE COMPOUND SELECTED FROM THE CLASSREPRESENTED BY THE FOLLOWING GENERAL FORMULA: